Materials and methods for production of aggregate-based tooling

ABSTRACT

A method for forming a composite structure, using a mandrel that is later removed from the composite structure, involves production of a mandrel by depositing a particulate mixture, including an aggregate and a binder, into a mold and removing the mandrel from the mold. The mandrel may be treated while still in the mold by heating, curing with an agent, microwave energy, or by some combination thereof. Once finished, the mandrel can be used in manufacturing polymer and/or composite components. The mandrel can also be include materials that can be easily removed from the finished composite structure by water, shakeout, chemically dissolving, or by some combination thereof

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part application of U.S. patent application Ser. No. 12/170,297, filed Jul. 9, 2008, which claims priority to U.S. Provisional Patent Application No. 60/949,765, filed on Jul. 13, 2007, and also claims priority to U.S. Provisional Patent Application No. 61/184,610, filed on Jun. 5, 2009, all of which are incorporated herein by reference in their entireties and made part hereof. This application is further related to U.S. patent application Ser. No. 12/793,868, filed concurrently on Jun. 4, 2010, which is also incorporated herein by reference in its entirety and made part hereof.

FIELD OF THE INVENTION

The present invention relates to a process and method for producing composite parts. In particular, this invention relates to mandrels for the mass production of polymer or composite structures, and to materials and methods for forming such mandrels at sufficient rates for mass production, as well as materials and methods for production of tooling using 3D printing techniques.

BACKGROUND OF THE INVENTION

Composite materials, such as fiber-reinforced composites, can be used to produce corrosion resistant and lightweight structures. “Composite material,” as used herein, refers to a material comprised of two or more separate materials, which may include a fiber or polymer binder or a combination of the two. The most common composites are normally comprised of a fiber (Glass, Kevlar, Carbon, etc) impregnated with a polymer (Epoxy, Polyester, Urethane, etc). In comparison to lightweight metals such as aluminum, structures formed of composite materials have high strength-to-weight and high stiffness-to-weight ratios. As a result, composite materials have been used to fabricate a wide variety of structures including, most notably, aircraft structures.

In the aircraft industry, composite components were initially limited to secondary structures such as floorboards and engine cowlings due to limited experience with designing composite structures. However, as the mechanics of composite materials became better understood and higher quality materials were developed, its use increased as primary aircraft components such as flaps, wing sections, and even as the entire fuselage.

Currently, aircraft exist that have a fuselage and wings made substantially or entirely from composite materials. Aircraft manufacturers have increased their dependence upon composite materials to meet their ever-increasing demands for improved efficiency and lower costs. Composite materials also are used in automotive, recreational, military and defense applications, where the performance requirements may be even more demanding.

A significant drawback to the use of composite structures in aerospace applications, whether commercial or military, is the complicated and expensive tooling that is required for their fabrication, particularly when a seamless, hollow structure is desired. To form a seamless, hollow composite structure, the use of a mandrel or mold core is often preferred. The composite materials, generally fiber and resin, are laid up on the mandrel and cured by applying heat, time and pressure according to well-known methods. For many applications, the mandrel is a single use mold/tool that is destructively removed from the finished part either by a chemical process or by mechanical agitation.

Mandrels for composite structures are often made of plaster. Plaster easily pours into a mold and forms a solid structure but requires a significant curing time. Moreover, plaster is generally removed by mechanical agitation which can result in damage to the composite structure, after which the material is discarded as waste.

Other conventional materials used for making tooling such as mandrels include eutectic salts. These materials pose certain processing problems associated with removal of the materials from the cured parts, as well as with the disposal of the materials. Salt mandrels are brittle and must be cast into the desired shape while molten to avoid the need to machine them. Moreover, despite being soluble in water, eutectic salts produce corrosive, environmentally unfriendly waste streams when washed from the cured composite part.

An alternative method for producing a seamless, hollow composite part is to use an inflatable bladder as a mandrel within a reusable female mold form. Such a method is disclosed, for example, in U.S. Pat. No. 5,366,684. Upon inflation, the bladder presses the laid-up composite into the female mold form. The bladder process, however, is not useful for complex shapes and does not produce a composite structure with the same accuracy as a more conventional molded mandrel, particularly where the internal dimensions of the part are critical.

More recent improvements in mandrel materials provide organic and inorganic binders that are environmentally benign and water-soluble. The mandrel material is a composite blend including a matrix, such as sand, a binder, and water. One such binder is polyvinylpyrrolidone, or “PVP”. The composite blend is prepared to a desired consistency, formed into a desired shape and cured. The resulting mandrel is strong and lightweight and easily can be shaped and subsequently removed from cured composite parts. Additives may be added to enhance the functional characteristics of the finished tooling material. These types of mandrel materials are disclosed, for example, in U.S. Pat. Nos. 6,325,958 and 6,828,373, both of which are incorporated by reference herein.

Utilizing the above processes (excluding the bladder technique) mandrels are currently formed using similar techniques, which involve the use of either a pourable material, such as eutectic salt or plaster, or a compressible material such as PVA and aggregate or sodium silicate and aggregate. Each of these processes can be very labor and time intensive.

Eutectic salts mandrels require the salt to be melted at temperatures in excess of 350° F. and, once molten, must be manipulated into a mold where it must cool and set for extended periods of time, often causing burns unless special protective clothing is worn. Further depending on the complexity of the mold and exposed cross section, significant amounts of water and time are needed to remove the eutectic salt from the mold, which also creates a highly corrosive waste stream.

Plaster is a more user friendly material, in that it can be prepared at room temperature and poured into a complex mold, but it also has several disadvantages. Since plaster is formed from the hydration of dehydrated salts, it is prepared from a dry powder material that is combined with water, which must be agitated to ensure proper mixing of the powder and water. This agitation leads to the formation of air bubbles within the material that can form significant defects in the resultant mandrel. Further, the plaster must be allowed to set, which is controlled by the temperature that the plaster is mixed at, as well as by additives to the mixture. Since this is normally a manual process, set times are around 10 min and can take as long as 45 min. Once set, the mandrel can be removed from the mold, but is not ready for composite layup, since it still contains significant amounts of water. This water must be removed to a sufficient level so as not to react with the composite system when the part is brought to temperature. Plaster is extremely time and energy intensive to dry since it forms a dense egg shell like skin, which acts as a heat and water barrier. Once a finished composite part is formed, the plaster material is either partially or completely water insoluble. Mechanical methods are then used to remove the mandrel often damaging the composite due to delamination.

Prior works have attempted to produce a water soluble plaster material that aids in the removal of the core from the finished composite part, but has come at the cost of reduced strength in the core. Further since these water soluble plasters still incorporate large amounts of water to pour the material there is a significant amount of time and energy needed to cure and dry the core.

Existing compressed material mandrels are comprised of moist sand-like materials that are packed or compressed into a mold to form the required shape. These materials can be labor intensive or require expensive tooling since the materials must normally be packed at high pressure to ensure uniformity in the mandrel. Further, complex shapes are very difficult to form since the materials are not very flowable and, as such, don't tend to fill molds with reverse cavities. However, since these materials start out with a very low density and open porosity, they can be readily dried or cured using a variety of techniques, for example CO2 curing, hot gas infiltration, vacuum drying, microwave or oven drying.

While these prior art practices provide improvements that have shortened processing time and overall costs, the manufacturing cost of a composite structure is still relatively high. Consequently, there remains a need for a simplified method for manufacturing composite parts. In particular, a need exists for simplified methods of formation of mandrels and for removal of mandrels from a seamless, hollow composite part.

Tooling for production of polymers, composites, and other materials can be produced using 3D printing techniques, including typical powder bed layer printing technologies such as those produced by Prometal, Z-Corp, and others. These machines lay thin layers of solid binder and/or aggregate onto a build plate which is then wetted in precise patterns utilizing an inkjet print system to disperse water-based or other fluid-based binder solution. Early 3D printing materials and methods are described in U.S. Pat. Nos. 5,204,055 (Sachs et al.), No. 5,340,656 (Sachs et al.), and No. 5,807,437 (Sachs et al.), all of which are incorporated by reference herein in their entireties and made part hereof. Current powder methods within the industry utilize slow curing processes that require either heat activation or a long residence time in the printer after the print has completed (usually on the order of an hour).

There is a need for easily removable tooling materials that can readily be fabricated at low cost and removed quickly and efficiently. Prior techniques for the manufacturing of water soluble mandrels for composite manufacturing have utilized organic polymer binders and cenospheres. For example, U.S. Pat. No. 6,828,373, also incorporated by reference herein in its entirety and made part hereof, discloses the production of water soluble mandrels that contain water soluble PVP binder coated over a cenosphere media utilizing water as the solvent. Alternative aggregate-binder systems have also been developed for foundry applications.

Soluble silicate based binders have been utilized within the foundry industry for the production of acid cured cores. Commonly an acid gas (e.g. CO₂) is utilized to neutralize the caustic that keeps the silicate in solution. Upon neutralization, an immediate precipitation of the silicate forms interconnecting bonds to the surrounding aggregate. This continuous matrix forms the structure of the core. This process has since been replaced with amine based chemistry in the modern foundry.

Several powder solidification chemistries through hydration have been proposed, for example as discussed in U.S. Patent Application Publication No. 2004/0038009, which is incorporated by reference herein in its entirety and made part hereof. This process utilizes an acid to induce cross linking in an organic binder system which produces relatively rapid solidification of the pattern upon hydration. Previous works have also utilized materials such as starches or plasters to form a hardened solid.

SUMMARY OF THE INVENTION

In one broad aspect, the invention relates to the production of complexly shaped mandrels with high precision without a pourable material that contains excess water. According to this aspect, the invention further eliminates the difficulties associated with mandrels produced by compression of materials such as by means of mechanical compaction that can result in uneven form filling. The above problems can be mitigated by transforming the aggregate/binder mixture into a fluidized state by application of kinetic energy to the mixture. In one embodiment, kinetic energy is imparted into a non liquid mandrel material, such as a binder/aggregate mixture, through a carrier fluid (most commonly a gaseous fluid such as air or nitrogen), by which the solids are able to be displaced as a semi fluid. Once in the semi fluid state, the mixture can then be directed/injected/blown into a mold in a similar fashion as a pourable material. As the material enters the mold, the carrier fluid is removed through properly placed vents while the material is remains contained in the mold. This technique affords the fast production of aggregate based mandrels that can readily be dried/cured using a host of processes, such as gas cure or heat drying.

In general, aspects of the present invention relate to methods of manufacturing composite structures wherein high quality mandrels can be produced in a relatively short period of time. Various arrangements for forming and curing mandrels are disclosed that may be used in an industrial or automated process whereby a large number of high quality mandrels may be made quickly and inexpensively.

Other aspects of the present invention relate to a method for forming a composite structure using a mandrel, wherein the mandrel is mass produced in a mold by filling the mold with a particulate mixture, including one or more aggregates and one or more binders, and removing the formed mandrel from the mold while the mandrel is still partially green, i.e. before reaching full cure. According to further aspects, the mandrel may be fully set or cured while still in the mold e.g. by heating, vacuum, curing with an agent, microwave energy, or by some combination thereof, or simply time.

Additional aspects of the invention relate to mandrel material compositions that can be cured quickly, thereby facilitating a mechanized or automated process for mandrel mass production. Further aspects of the invention relate to mandrel material compositions that may provide mandrels having sufficient strength with little or no curing such that the mandrel may be handled, stored, or shipped, wherein curing may be completed at a later time or even over time during the course of storage or shipment. Further, the invention may make use of other currently available water soluble binders for producing composite mandrels depending on the necessary properties.

Still further aspects of the invention relate to methods of manufacturing composite structures wherein the mandrel materials may be environmentally benign and water-soluble. Moreover, aspects of the invention allow for the reclamation of mandrel materials for reuse to further reduce costs and minimize the impact on the environment.

Aspects of the invention also relate to a composition for use in manufacturing a water-soluble tooling material using a 3D printing apparatus. The composition includes an organic binder material that is water soluble after curing, an alkali silicate binder material that curable by acid gas curing to produce a water-insoluble structure, and an aggregate material. The organic binder material may be polyvinylpyrrolidone and the alkali silicate binder material may include sodium and/or potassium silicate. Additionally, the composition may be provided as a powdered mixture configured for use in a 3D printing apparatus, which mixture may have a particle size of between about 20 microns and about 150 microns, a volume fraction of powder from about 50% to about 99% by weight, and a mean maximum particle aspect ratio of less than 3:1. In another embodiment, the organic binder and/or the silicate binder may be provided in an aqueous solution that is configured to be deposited on the aggregate material. The alkali silicate binder material may be present in sufficient amount to enable handling of a part produced from the composition after acid gas curing and without curing of the organic binder material, and the organic binder material may be present in sufficient amount to enable the part to be removed completely using application of water.

According to one aspect, the composition includes, by weight, from about 1% to about 10% polyvinylpyrrolidone and from about 1% to about 30% alkali silicate.

According to another aspect, the composition includes, by weight, 1-55% alkali silicate, about 3-70% polyvinylpyrrolidone, and about 20-90% aggregate material. In another embodiment, the composition may include about 15% potassium silicate, about 30% polyvinylpyrrolidone, and about 55% aggregate material.

According to further aspects, the organic binder material may include a protein or salts of carboxymethyl cellulose (SCMC). Where the binder includes salts of carboxymethyl cellulose, the composition may include between about 0.5% and 40% by weight thereof. Additionally, the salts of carboxymethyl cellulose include at least one cation, such as H+, Na+, K+ Ca2+, and combinations thereof, and a degree of substitution of carboxymethyl cellulose groups per anhydroglucose chain may be between 0.5 and 0.9.

According to yet another aspect, the alkali silicate binder material has an alkali caustic to silicate ratio of 3:1.

According to a still further aspect, the composition has a ratio of alkali silicate binder to organic binder of about 1:1 to 3:1, by weight.

Further aspects of the invention relate to a powdered mixture for use in manufacturing a water-soluble tooling material using a 3D printing apparatus, which includes, by weight: from about 1% to about 55% alkali silicate, from about 3% to about 70% polyvinylpyrrolidone, and from about 20 to about 90% aggregate material. In one embodiment, the powdered mixture has a particle size of between about 20 microns and about 150 microns.

Other aspects of the invention relate to composition for use in manufacturing a water-soluble tooling material using a 3D printing apparatus, which includes, by weight: about 10-20% alkali silicate, about 25-35% polyvinylpyrrolidone, and about 50-60% aggregate.

According to one aspect, the composition comprises about 15% potassium silicate, about 30% polyvinylpyrrolidone, and about 55% aggregate material.

According to another aspect, at least one of the alkali silicate and the polyvinylpyrrolidone is provided in aqueous solution.

The products and methods described herein are especially useful for forming mandrels for producing lightweight composite structures, e.g. for the transportation industry, such as aircraft or aerospace industry, and will be described in connection with such utility, although other utilities are contemplated.

BRIEF DESCRIPTION OF THE DRAWINGS

To understand the present invention, it will now be described by way of example, with reference to the accompanying drawings in which:

FIG. 1 is a schematic diagram of one embodiment of a system for mandrel fabrication using a pressurized material injection vessel;

FIG. 2 is a schematic diagram of another embodiment of a system for mandrel fabrication using a pressurized material injection vessel and a pressing mechanism;

FIG. 3 is a schematic diagram of a further embodiment of a system for mandrel fabrication using a mold injection apparatus and a pressing mechanism;

FIG. 4 is a schematic diagram of one embodiment of a mold for use with mandrel forming methods according to the present invention;

FIG. 5 is a schematic diagram of one embodiment of a method for drying/curing a binder and aggregate composition within a mold;

FIG. 6 is a schematic diagram of one embodiment of a multi-step method for drying/curing a binder and aggregate composition;

FIG. 7 is a schematic diagram of one embodiment of a method for production of a composite part according to the present invention;

FIG. 8 is a schematic diagram of one embodiment of a system for mandrel fabrication using a pressurized material injection vessel and a distribution manifold; and

FIG. 9 is a schematic diagram of one embodiment of a system for tool fabrication using a powder 3D printing apparatus.

DETAILED DESCRIPTION

Further features and advantages of the present invention will be seen from the following detailed description, in which is shown various embodiments of the present invention. It is understood that other embodiments may be utilized and changes may be made without departing from the scope of the present invention.

The present invention relates to devices and methods for forming mandrels for use in the production of hollow composite structures, which devices and methods may be used for mass production of such mandrels. The mandrels are typically made from sand or other aggregate held together in the desired shape by means of a binder, and may include additional ingredients as well. In one embodiment, the process used to form the mandrel comprises mixing the aggregate with the binder, forming the mixture into the desired shape, then treating the mixture so that the binder hardens sufficiently so that the mandrel can be handled.

In various embodiments of the present invention, an aggregate material and a binder material, mixed to form a non-fluid aggregate/binder mixture, can be fluidized by imparting kinetic energy to the mixture, which allows the mixture to be inserted into a mold in a fluid manner. It is understood that the aggregate material and the binder material may contain more than one aggregate or binder, respectively. This aggregate/binder mixture may have a moist sand-like consistency in some embodiments. In one embodiment, such a non-fluid mixture may be fluidized by imparting kinetic energy into the mixture through entraining the mixture in a carrier fluid (such as air or nitrogen), allowing the solids to be displaced as a fluid. Once in the fluidized state, the mixture can then be directed/injected into a mold in a similar fashion as a pourable material. As the material enters the mold, the carrier fluid is removed, such as through properly placed vents, while the non-fluid mixture remains and is contained within the mold, filling the mold. Such techniques can afford the fast production of aggregate based mandrels that can be readily be dried/cured using a host of processes, such as gas cure or heat drying, as described below. It is understood that other means and techniques for fluidizing the aggregate/binder mixture may be used in accordance with the present invention. It is also understood that fluidizing the mixture involves causing a non-fluid material to behave in a fluid manner, but does not include transforming the material into a fluid phase (such as a liquid or gas).

In one exemplary embodiment, the aggregate/binder mixture can be carried into a mold using a pressurized material injection vessel 100 (e.g., a sand blaster), as illustrated in FIG. 1. The aggregate/binder mixture 105 is first placed into the sand blaster tank 104, and the tank 104 is sealed and an air supply 101 is connected thereto. The air supply 101 is split to provide air to the tank 104 through an entry valve 102 and also to a mixing valve 107 located downstream from the tank 104, through a separate line 103. When the entry valve 102 is opened to the system, air 111 is forced through the tank 104 toward the exit orifice 106 at the base of the tank. The aggregate mixture 105 is propelled along with the air 111 out of the tank 104 toward the mixing valve 107. As the aggregate mixture 105 enters the mixing valve 107 it is mixed with air from line 103 and propelled out into a fill tube 108 which directs the mixture to the cavity of a mold or tool 109. The aggregate mixture 105 collects in the mold and forms a mandrel in the shape of the mold 109. The second air stream (from line 103) that is passed through the mixing valve 107 may be forced at a sufficient rate so as to induce a venturi effect on the tank orifice 106, which helps draw the aggregate mixture into the air stream.

Once the aggregate mixture is entrained in the air stream, the aggregate can be directed as a fluid into a range of molds or properly vented housings for the ultimate production of the desired shape, such as the mold 109 shown in FIG. 1. Vents 112 within the mold 109 allow the fluidized material to move to the desired region in the mold 109, at which point the aggregate mixture 105 is separated from the air stream, which exits the mold to the environment, illustrated by arrows 110. In this embodiment, it may be desirable to mechanically agitate the sand blaster's tank 104, where the mixture 105 is stored, to ensure that the aggregate mixture 105 does not bridge as material is removed from the chamber, causing air pockets in the exiting stream. In one embodiment, after filling the mold 109, the fill tube 108 for the mold 109 can be used to infiltrate the mold 109 with a cure gas to cure the mandrel (as described below) using the same flow path as the injection of the mixture 105. Other gassing configurations are also possible, as well as other non-gaseous curing techniques.

In another embodiment, the injection vessel 100 of FIG. 1 can be combined with a compaction system 120 as shown in FIG. 2. Similarly to the process discussed above the injection vessel 100 is utilized to propel the aggregate/binder mixture 105 into the mold fill line 108. In this embodiment, the material is directed into a mold 121 that is held in place under force from an external press 122. As in the mold 109 described above, the fluid is able to escape from the mold 121 through vents 123, while the mixture 105 remains in the mold 121. Once the mixture 105 has filled the mold 121 and the fluid has exited completely through the vent system 123, additional compaction of the formed mandrel can be accomplished through increased mechanical force using the external press 122. In this embodiment, the mold 121 is specifically designed to allow the cavity of the mold 121 to be filled and then compressed further to a final strength. The mold 121 may thus include complementary surfaces designed to allow room for parts of the mold 121 to move during compression. This configuration can create additional compaction and densification of the mandrel material. Although a vertical press configuration is shown, other types of pressing configurations may be used, including horizontal or isostatic pressing.

In a further embodiment, an aggregate mixture can be carried into a mold using a pressurized material injection vessel 200 to inject the material directly into the mold, as shown in FIG. 3. As similarly described above, a mixture 204 of an aggregate material and a binder material is prepared and placed into an aggregate mixture chamber 202. The chamber 202 is connected to a cavity 208 of a mold or tool 206 to allow the contents of the chamber 202 to flow into the mold 206. A volume of air or other fluid 203, from a pressurized source 201, is passed through the aggregate mixture chamber 202, forcing the material 204 out of the chamber 202 and into the mold 206. In a configuration such as shown in FIG. 3, a higher kinetic energy can be imparted to the aggregate mixture by significantly increasing the flow rate of the fluid 203 that is able to enter the aggregate mixture chamber 202. Vents 207 within the mold 206 allow the fluid to exit the mold 206 and flow into the environment after distributing the material throughout the mold cavity 208, while the material 204 remains in the mold cavity 208.

As shown in FIG. 3, a mechanical press 205 can also be applied to the mold 206, which is used to hold pieces of a multi-piece mold together. As also described above, although a vertical press configuration is shown, other types of pressing configurations may be used, including horizontal or isostatic pressing.

Assemblies such as those shown in FIGS. 1-3 can be used as a mandrel making machine capable of mass producing mandrels, which are, in turn, used to produce composite parts. A mixture of sand or other aggregate with a binder is prepared and injected into a mold, such as in a manner described above. The mixture may advantageously be prepared to a consistency that allows the mixture to completely fill the mold without a void. One exemplary mold 300 is shown in FIG. 4. The mold 300 includes two mold halves 301, 302 that are pressed together to form an internal mold cavity 303 for formation of a mandrel 304. Each mold half 301, 302 contains at least one inlet port 305 for injection or inlet of material such as in the manners described above with respect to FIGS. 1-3, and at least one outlet port 306 to allow fluid to escape therefrom after the aggregate mixture is deposited within the mold cavity 303. In the embodiment shown, the mold 300 includes multiple inlet ports 305, which may be provided by a manifold, as described below. It is understood that in some embodiments, only one of the mold halves 301, 302 may contain an inlet port 305 and/or an outlet port 306. It is also understood that a different mold configuration may be used to form a mandrel.

FIG. 8 illustrates an exemplary embodiment of a system 700 for distribution of the fluidized aggregate mixture 701 into a mold 702 using a pressurized material injection vessel 703 (e.g., a sand blaster), which, in this embodiment, is similar or identical to the injection vessel 100 shown and described in FIG. 1. In the embodiment shown in FIG. 8, the injection vessel 703 has a hose 704 coupled to a manifold 705, and the manifold 705 is coupled to the mold 702 and distributes the flow of the aggregate mixture 701 to provide multiple injection ports 706 for injection of the mixture 701 into the mold cavity 707. The cavity also has outlet ports 708, as depicted in FIG. 6. Further the initial injection vessel 703 may contain multiple output ports so as to supply multiple injection ports 706 in the mold 707.

In different embodiments, the mold may be configured with either horizontal or vertical parting lines. Additionally, in one embodiment, the mold has a single parting line, but in other embodiments, the mold may have multiple parting lines. For example, a mold with multiple vertical parting lines may include multiple injection devices to accelerate the process. Some mandrel shapes, however, may be better suited for production in horizontal parting line molds. For example, horizontal parting line molds may be more suitable when large mandrels are to be produced in one mold, so that the cavity for forming the mandrel extends relatively far from the injection means. Similarly, if several mandrels were to be made simultaneously using a mold with multiple cavities, a horizontal parting line mold may offer better performance.

The mixture is injected into the mandrel form (mold) by an injection means, such as the injection means discussed above. If necessary, water or another liquid may be added to the material such that a desired viscosity is reached for “shooting” the mixture into the mold. The injection means may utilize compressed air, gravity, or any other means capable of mobilizing or fluidizing an aggregate/binder mixture. The injection means may additionally be used to inject the mixture into multiple molds at a time.

Once the mold has been filled with the aggregate/binder mixture, one or more processing methods can be adopted to process the mandrel into a desired state for use in polymer or composite manufacturing. Generally, the filled mold is treated to activate the binder in the mixture or to otherwise harden the mixture such that the mandrel retains its shape upon being removed from the mold. In one exemplary embodiment, the process of treating the mandrel is designed to take a very short period of time, such as on the order of seconds, so that the formed mandrel may be removed from the mold and the mold may be filled again rapidly, facilitating a process capable of being used to mass produce mandrels. In certain embodiments, the entire process of molding the mandrel can take less than two minutes, and in one embodiment, less than one minute. Depending on the composition of the mixture used, and, in particular, the type of binder(s) used, the mandrel may be treated initially by one of a number of methods.

One embodiment of such a treating method is fluid exchange dehydration, an example of which is illustrated in FIG. 5. As shown in FIG. 5, a drying gas 401, such as air, is passed into the mold 404, where it contacts the moist material forming the green mandrel 406, picks up moisture, and exits through vents 407 in the mold 404. The mold may include one or more inlets and one or more outlets for the stream of gas to pass into and out of the form and may pass over the mandrel in multiple directions to shorten the duration required for treatment. As described above, in one embodiment, the same inlets and outlets used when filling the mold with the aggregate mixture can be used for infiltrating the mold with the drying gas.

In some embodiments, maintaining low water vapor pressure and relatively high temperature in the drying gas stream 401 can increase the rate of removal of water or other liquid. Heating the mandrel 406 through the mold 404, as described in the hot-box techniques below, can also increase the rate of liquid removal. This will further reduce the treating time and curing time of the formed mandrel, and can increase mass production rate. In addition, a vacuum (not shown) can be advantageously applied to exit vents 407, along with any of the above-described configurations. In one embodiment of this technique, a hot gas is heated to about 150° F.-250° F. and passes through the mold for a period of about 30 seconds to two minutes. It is understood that this time may be varied depending upon the temperature of the hot gas, the mixture composition, the size of the mandrel, and the configuration of the mold in allowing hot gas to pass over the mandrel. In another embodiment, a similar drying technique would utilize only bone dry gas or a combination of both dry and hot gas to dry the mandrel through dehydration/evaporation. Materials that can be subjected to dehydration in this manner include inorganic salts (sodium silicate, phosphates, MgSO₄, etc) and organic binders (PVP, PVA, protein etc).

In another embodiment, a cold-box or no-bake method, such as a reactive gas curing method, advantageously may be used to treat the green mandrel, wherein the cure of the mandrel can take place without heating the mold. This is typically effected by exposing the mandrel to a curing agent, usually in gaseous form. For example, if the binder is acid curable, a vaporized amine solution or carbon dioxide vapors may be used. The configuration illustrated in FIG. 5 can be used for a reactive gas curing technique as well. In such an embodiment, instead of applying a drying gas to remove water from the mandrel 406, a reactive gas 402 can be introduced into the mold in addition to, or in place of, the drying gas 401. The reactive gas 402 forces a phase change or reaction within the binder of the mandrel, which then produces the desired strength in the mandrel. Depending on the binder and the curing agent, this process typically takes a very short time, and may take less than 30 seconds. In one embodiment, the treating process with a curing agent may be completed in 10 seconds or less. Many different types of binders are usable with reactive curing techniques, including sodium silicate, Isocure™, or any other binder system that undergoes a chemical reaction to reach a hardened or semi-hardened state.

A further embodiment of a treating method that advantageously may be used to cure/strengthen the mandrel is a hot-box method, wherein the mandrel materials are hardened by heating the mold. This effectively removes liquid (such as water) from the formed mandrel and hardens certain binder materials, including many water-soluble binders and non-water-soluble binders. One such means of heating the mandrel 406 is application of internal microwave energy 405 or other heating energy within the mold 404, as illustrated in FIG. 5. Accordingly, in one embodiment, the mold 404 may be constructed of materials that allow the mandrel 406 to be exposed to microwave energy 405 while still in the mold, such as PVP or PVA or other dehydration strengthening binders combined with a porous aggregate. The heating treatment generally takes place at least long enough for the mandrel to achieve sufficient green strength to enable handling without damage to the mandrel or its shape. This can take anywhere from several seconds to minutes. If the mandrel is not fully dried before removal from the form, further drying of the mandrel, which may be required before lay-up of composite fiber and resin, can take place over time during storage or shipment, as described below. For this method of treating, it may be advantageous for the mold to comprise a material with a high thermal conductivity, such as steel, aluminum, Invar, etc.

Certain mixtures may have sufficient green strength to be removed from the mold almost immediately after loading or after a very short treatment under one of the methods listed above. The curing process for these mandrels may continue as the mandrels dry in storage or shipment, as described above, or the curing process may be further effected by some other means. For instance, curing may be completed by exposing the mandrel to a curing agent, baking the mandrel in an oven, or irradiating with microwave energy. This secondary treating process may further enhance the overall efficiency of the mandrel production process.

One example of such a two step curing process is shown in FIG. 6. An initial strengthening technique 501 is used to impart the mandrel 505 with sufficient strength to be removed from the mold 502. The hot gas drying, hot-box, or cold-box reactive curing techniques described above can be used, for example, as the initial strengthening technique 501. After the initial strengthening, when the mandrel material has reached sufficient strength for handling, the partially-hardened or partially-cured mandrel 505 is removed 504 from the mold 502 and placed 506 into a secondary treatment process 507 for further strengthening. Such a secondary treatment process 507 may include, without limitation, convection oven heating, exposure to electromagnetic waves (such as microwave heating), chemical reaction, exposure to another energy source not listed above, placing in a vacuum chamber, placing in a dry environment, placing in a shipping container with or without a desiccant, or any mixture of such techniques.

For example, in one exemplary embodiment, the mandrel material mixture contains a primary binder that provides good strength and desirable properties and a secondary binder that strengthens quickly to permit removal of the mandrel from the tooling before the primary binder is hardened. As described above, the primary binder can be hardened after removal, leaving the mold free for production of additional mandrels, increasing production rate. In one embodiment, the mixture includes a primary binder that is water-soluble and environmentally benign, such as polyvinyl pyrrolidone (PVP), and an additive that may be treated with a gas, such as sodium silicate, also called water glass. Uncured PVP has very little green strength and is generally cured by a hot-box process which requires that the mandrel remain in the mold during this process. The water glass component of the binder, however, may be quickly fixed by passing carbon dioxide (CO₂) or any other slightly acidic gas through the mold for only a few seconds, after which the mandrel retains sufficient strength to allow handling. In this manner, the mandrel may be removed from the mold and cured using microwave energy. The microwave energy cures the mandrel in only a few seconds, after which the dry strength of the PVP provides a durable mandrel that is relatively lightweight and water-soluble.

A mandrel mixture composition according to the present invention may typically include sand and/or other aggregate(s), a binder or combination of binders, and possibly additional additives to improve the characteristics of the mandrel in a particular application. In many embodiments, the water soluble binder/aggregate mixtures have binder concentrations that range from less than 0.5% binder to weight of aggregate to over 50%. The amount of binder utilized can be determined by the desired ultimate strength and drying time. Additionally, in some embodiments, water content in the binder/aggregate mixture is kept to a minimum, in order to facilitate drying/strengthening of the mandrel. For example, water contents of less than 10% are typical of some embodiments. Further, in some embodiments, it is preferable for the aggregate and binder mixture used to produce the mandrel to possess a porosity greater than about 20%. Too low a porosity within the uncured mandrel material can lead to the formation of steam pockets within the mandrel that can produce pathways in the mandrel or even complete deformation.

Various different aggregates, or combinations thereof, may be used in different embodiments of the binder/aggregate mixture. Sand is one suitable choice for the aggregate component of the mixture because of its availability. However, other aggregates may be chosen for various reasons, such as their compatibility with a particular binder, their consistency, or their capacity to undergo a reclamation process after being removed from the finished composite structure. Examples of other particulate materials which may be employed as aggregates or as additives include glass or polymer microspheres, pumice, graphite or coke particles, small steel shot, glass beads or bubbles, small polypropylene pellets, alumina, cenospheres, and clays. A combination of two or more of these materials may also be used. Particle size is often directly related to surface quality, aggregate density, and packing density, and in one embodiment, particle sizes of between about 100 microns and about 300 microns are utilized. The resultant aggregate density can vary from about 0.4 to about 2 g/ml, in one embodiment. Higher aggregate densities can results in higher compaction, but may not be ideal for some applications, since particle size also plays an important role. Other density considerations may include mandrel geometry, since higher density aggregates can result in higher stresses being exerted on the mandrel.

A binder or combination of binders can be chosen based on a number of factors, including the duration of time required to treat the mandrel until it reaches a level of hardness to allow handling, the tensile strength of the binder in connection with the chosen aggregate when fully cured, the cost of the binder, the viscosity of the mixture when the binder and aggregate are combined, the water-solubility of the binder, and the environmental byproducts of the curing and removal processes. Ultimately, the proper binder can be determined with reference to the specific properties necessary for the finished composite part. Certain mixtures of salts and aggregate produce a fairly weak and brittle mandrel that is not readily usable in most composite preparation techniques, but will withstand the conditions necessary for a wet lay-up of composite material. Such a low strength salt mandrel can be prepared quickly and inexpensively using currently available binders and machinery. Tensile strengths for this type of mandrel are usually on the order of 100 PSI. These binders include, but are not limited to, MgSO₄, phosphates, sodium silicate, etc.

Other applications may be better suited to different binder systems. For example, in more demanding applications and in mandrels that may require secondary machining after fabrication, a range of hybrid systems may be used for manufacturing the mandrel, including, but not limited to, combinations of organic and inorganic binders. As described above, in one exemplary embodiment, a water-soluble hybrid binder composition includes sodium silicate and PVP. For example, such compositions can range from about 1-20% weight sodium silicate and about 1-30% weight PVP, in various embodiments with the remained being comprised of aggregate and/or additive. In other embodiments, the binder composition for mixture with an aggregate may include from about 3-30% PVP and from about 3-40% alkali silicate, or from about 1-30% PVP and from about 1-40% alkali silicate. Such compositions may also include 7-17% water. Specific binder compositions and ratios may vary, dependent on factors such as the aggregate type and size and the effective surface area of the binder. In many embodiments of hybrid compositions, the organic component affords a mandrel with better machinability, which also is capable of attaining higher strengths for demanding applications. PVP is one such suitable organic binder, due to properties such as water-solubility, low viscosity, high tensile strength, and environmentally benign nature. Many other water-soluble binders may be used with other embodiments, including but not limited to various salts (including sodium silicate), phosphates, gelatins, water-soluble hemicellulose, water-soluble polymers, and poly vinyl alcohol. Other non-water-soluble materials may also be appropriate as binder materials, including phenolics and many organic polymers.

Various specific compositions have been found to have advantageous properties when used in connection with the production methods described herein. One exemplary binder/aggregate composition includes about 3-10% PVP, about 3-10% liquid sodium silicate, (40 baum), about 7-17% water, and about 70-77% cenospheres. This composition produces a high strength, acid gas-curable mandrel material having good green strength with average coefficient of thermal expansion (CTE) less than 10 ppm. Additionally, the mandrels resulting from this composition generally have good surface finish and water solubility. Another exemplary composition includes about 3% PVP, about 17% water, and about 80% cenospheres. This composition must be dried to gain green strength and has similar CTE values to the immediately preceding composition. Additionally, the mandrels resulting from this composition generally have good surface finish and are highly water soluble. A further exemplary composition includes about 20% sodium silicate (40 baum) and about 80% cenospheres. This composition is a very fast acid gas-curable composition, and is water-insoluble at room temperature. It also produces mandrels with good surface finish.

Additives may be used to enhance the performance of the mandrel and materials in any of the above embodiments. Such materials include alkaline hydroxides, e.g., NaOH, water and various organic and inorganic additives. Less than 1% additives is necessary in many exemplary compositions. Minor amounts of other additives, such as surfactants, may be present. The surfactants may be anionic, nonionic, cationic, amphoretic or mixtures thereof. Examples of water soluble surfactants are anionic surfactants selected from organic sulphates, organic sulphonates and organic phosphate esters, e.g., potassium 2-ethylhexyl phosphate. Certain surfactants also operate as flow control agents. Other additives include humidity resistant additives, collapsibility (or breakdown) enhancers, preservatives, dyes, bulking agents, hot strength additives, or flow enhancers. Humidity resistant additives include, for example, potassium tetraborate, zinc carbonate, zinc oxide. Collapsibility (or breakdown) enhancers include, for example, sugar, e.g., sucrose, dextrin and sawdust. Refractory coatings, such as silica in a solvent, may be used to impart a finished surface to the mandrel. Of course, the additives may be added in combination or singly.

Preservatives may be added to prevent mold and spoilage of the binders during storage. Amounts of such preservatives will vary depending upon the preservative employed, but generally, amounts up to about 1 percent by weight are considered sufficient. In one embodiment, sodium benzoate is used as a preservative, and is typically utilized in an amount of about 0.2 percent based upon the weight of the binder. Essentially any preservative which is compatible with the binder and various other additives and which is environmentally safe can be used in the present invention.

After treating and removing from the mold, a mandrel may require machining or other processing to form the desired shape. Depending on materials used and their cure, further curing may be required prior to machining the mandrel.

The invention further relates to methods for manufacture of composite or polymer parts or components, including complex parts such as ductwork which provides a passageway for channeling air, gases, fluids, wiring or the like. The type of composite or polymer product is, however, not a limiting feature of the invention. One aspect of the invention is the ability to manufacture composite parts at efficient rates, so that the parts can be effectively mass produced in an economic manner. In general, polymer or composite materials (including precursor materials) are placed into contact with the mandrel in order to impart the shape of the mandrel to the final polymer or composite product. One such production method involves wrapping the mandrel with materials to produce the final product. The mandrel can also be used for a range of other known processing techniques like plastic injection, RTM, VRTM, etc.

By way of example, in producing a composite product, a preformed mandrel of the type described above may be wrapped with or otherwise coated with a polymer or composite material (which may include precursor materials). The coated material may then be cured by heating, exposing to light energy, etc. Techniques for curing such polymer or composite materials are known in the art, and vary by the type and nature of materials used. Then the mandrel may be removed, for example by solubilizing in water, to open a formed passageway in the formed part. The mandrel, having been formed by efficient production speed techniques coupled with its use as a means to form the internal configuration of composites which are processable at efficient production speed levels enables the economic production of polymer or composite parts. The production efficiency can be further enhanced by the ability to remove the mandrel material from the composite part quickly, efficiently and without damage to the formed composite, such as through the use of water-soluble binders. Making the mandrels and using them with composites thus enables economic manufacture of complex composite and polymer parts, particularly those having complex internal hollows, chambers and passageways. For example, components such airducts and hollow structural components such as air frames, bikes and bike frames, car frames, and plane hulls can be manufactured using composite materials using the mandrels and methods described herein. Parts may be produced using the principles described herein for use in motor vehicles, boats, bicycles and other transportation vehicles, as well as other structures for various other industries. Examples of composite materials that can be used in accordance with embodiments of the invention include epoxy- or phenolic-based polymer binders impregnated into different fiber systems, such as fiberglass, Kevlar, carbon, etc. It is understood that these examples of components and materials are not exhaustive, and that a wide variety of components and materials can be manufactured.

FIG. 7 illustrates one exemplary embodiment of a production method 600 according to principles of the invention. The aggregate material(s) 601 are first mixed with binder material(s) 602, as well as potentially other additives, to form the binder/aggregate mixture 603. This mixture is then placed in a fluidized state by imparting the mixture in a carrier fluid 604. Once in the fluidized state, the mixture 603 and carrier fluid 604 are propelled via a pressure gradient into a mold 605 with a vented cavity. The material 603 enters the cavity through a fill port 605 a and is separated from the carrier fluid 605 using a screen or filter at the dedicated vents 605 b. After the cavity is filled with the material 603 to form the green mandrel 607, additional processing 606 is performed to facilitate removal of the mandrel 607 from the mold 605. As described above, this can accomplished in a variety of ways, ranging from complete curing within the mold or initial curing and removal for post drying/curing. Curing within the mold can be accomplished through techniques described above, such as removal of water (via heat, air, vacuum, microwave, etc.) or chemical reaction (crosslinking, precipitation, polymerization, etc.). Multi-step curing processes described above can also be used, where the mandrel 607 can initially be cured enough to gain partial strength for removal, forming a partially-cured or partially-hardened mandrel, and the partially-hardened mandrel can then be post-cured using any of the above techniques. The initial curing and removal can allow the mandrel to be removed and the mold recovered more quickly for continued processing.

After the mandrel 607 has been fully cured, it can then be used for producing a finished composite or polymer part. A release layer may be applied to the mandrel before part production, such as in the form of a sealer, which stops the resin/polymer systems of the composite or polymer product from penetrating the mandrel material. In the above illustration, the mandrel is covered with a polymer-impregnated fiber 608 to create a composite form 609 of the desired shape. Once in the desired shape, depending on the utilized resin/polymer system, the part may be cured, for example by using techniques such as vacuum, heat, UV, and chemical means. After reaching the desired cure state, the composite part 610 is then ready for mandrel removal. The part can be cured using any known technique, depending on the material, including without limitation application of heat, application of pressure, application of light or other electromagnetic wave, chemical reaction, exposure to another type of energy source other than the above, placing in a vacuum chamber, placing in a dry environment, or any combination of said techniques. The mandrel can be removed using a range of techniques from mechanical agitation to water dissolution, depending on the binder/aggregate composition. In one embodiment, where the mandrel 607 includes a water soluble binder composition, the mandrel is solubilized by application of water thereto, which breaks up the mandrel 607 and washes away the insoluble components of the mandrel, without damaging the produced article. The final product is a finished composite part 610 and the removed mandrel materials 611. In one embodiment, the aggregate and water may be reclaimed upon removal of the mandrel from the finished composite structure.

The invention further relates to methods for removing a mandrel from a finished composite part after the product has been molded and cured. Where a water-soluble binder is used, mandrels may be removed from a finished composite structure by exposing the binder and aggregate particles to an effective amount of water to dissolve the binder and disintegrate the mandrel, and then removing the aggregate particles from the cavity of the molded product. The environmental impact of water-soluble binders may be considered in choosing a method for removing the binder material, as not all of the byproducts of water-soluble binders are environmentally benign.

In one embodiment, the water may be sprayed into the structure at high pressure to remove the mandrel material more quickly. Alternatively, the water may be heated to a temperature below boiling which may dissolve particular binders more quickly. Yet another alternative would be to jet a stream of water into the finished composite structure to break the bonds of the water-soluble binder, and then removing any remaining mandrel material either with water directly or by mechanical agitation. Each of these methods can be performed in less than 30 minutes for most mandrels, and many mandrels may be fully removed in less than one minute.

With certain binders, the rate at which the bonded sand mandrel is weakened by exposure to water may be accelerated by pretreatment of the sand mandrel. In some exemplary embodiments, this pretreatment involves immersing the sand mandrel in a dilute alkaline solution or hot water for from one to ten minutes, drawing the alkaline solution or water through the mandrel, and/or blowing steam through the mandrel. The alkaline treatment is particularly suitable for composite materials which are not affected by alkali. Examples of useful solutions for this method include dilute alkaline solutions of sodium hydroxide, potassium hydroxide or sodium carbonate, which are relatively benign and relatively inexpensive.

Mechanical agitation also may be used to remove the mandrel from the composite structure. In one embodiment, the mandrel may first be conditioned by steam, water, or some other removal agent to initially break at least some of the bonds of the mandrel. A mechanical means may additionally or alternately be provided to break the mandrel into pieces while within the composite structure. Once the mandrel has been weakened by chemical or mechanical means, the finished composite structure is agitated by shaking or some other method to remove the rest of the mandrel material. This is a typical method of removal for most non-water-soluble binders, including various organic compounds and phenolics.

The invention also relates to mandrels produced using the above materials, methods, and machines. In one embodiment, a mandrel produced as described above includes a water-soluble organic or inorganic binder, or a combination of organic and inorganic binders, and one or more aggregate materials, such as sand, ceramic spheres, etc., as described above. It is understood that various embodiments of the mandrels described herein may contain any of the materials and additives described above for use in manufacturing the mandrels. Additionally, the mandrels manufactured as described herein can be used for the methods of forming composites described herein.

EXAMPLE

In one example, an air duct was created utilizing a bisphenol/epichlorohydrin-based impregnated woven carbon fiber pre-preg. A seamless air duct was formed by first producing an injection tool with the desired part shape machined into a splittable cavity. The tool was constructed to be ported to allow the carrier fluid to escape as needed. A binder/aggregate mixture was made by combining 80% cenosphere aggregate, 3% PVP, 3% sodium silicate (40 Baum) and 14% water. A green mandrel was then produced through injection of an aggregate/binder mixture into the carrier chamber under injection pressures of around 50 psi, with the carrier fluid being exhausted into environment. An acid gas (CO₂) was then passed into the tool cavity to partially harden the mandrel, under gas pressures of 40 psi or more, to ensure maximum contact with the mandrel. After 30 seconds of gassing, the tool cavity was split open and the mandrel ejected. The partially-hardened mandrel was then post-cured in a microwave oven for 90 seconds before sealing. Once sufficient water was removed, the mandrel was sealed, first utilizing a filler material (such as Holcote™) to close the mandrel's outer porosity and then finish coated with a plaster primer (such as Valspar™). After the sealer was completely dried, a release agent (such as Freecote™) was applied to the mandrel to aid in the release of the composite.

A prepreg composite material was then wrapped around the finished mandrel in a manner so as to produce uniformly distributed layers, as is familiar to those experienced in the art. After the composite material was laid up on the mandrel, a release layer was applied (such as Peel Ply, Pourous Release Film etc.). Then the mandrel was wrapped in a breather material, allowing a vacuum to be well-distributed around the mandrel. After the breather was applied, the mandrel was bagged in a vacuum-tight envelope and a vacuum was applied to the part. The part was then placed into an oven for curing at 150° F. for 1 hour. The resultant structure contains tightly packed carbon fiber with typically less than 40% epoxy, and the epoxy hardened to form a strong finished part. The part was then cooled, removed from the oven, and de-bagged, and the release layer was removed, leaving the finished part with the mandrel still intact.

To remove the mandrel, the part was submersed for several minutes in a container of water and rinsed out using jetted water. The mandrel was thereby dissolved and removed from the finished composite part, which was then allowed to dry, leaving a seamless hollow composite part. The total process from injection of the material to the finished composite part for this specific example was around two hours. The above example is intended to be a representative embodiment of the mandrel and methods described herein, and is not intended to be exclusive or limiting in any way.

Other aspects of the invention relate to materials and methods for producing a tooling material using 3D printing techniques. The direct printing of a water soluble part directly from a 3D printer allows for the production of a removable core. Removable cores and other tooling are useful in an array of industries, including composites and metal casting. Removable tooling can be produced using a non-soluble or low solubility powder material that is capable of rapid recovery from the printer after printing. Insoluble materials have been utilized to produce tooling with desired shapes in many industries, but such tools require less efficient and/or effective alternative removal techniques than water.

One broad exemplary embodiment of a 3D printing method described herein includes forming a powder layer from any of the below mentioned systems, onto which is dispensed an aqueous print solution in a predetermined, cross-sectional pattern. A print head, such as an inkjet printing head, can be used to deposit the print solution onto a powder bed to form the powder layer. The powder layer may contain a filler or aggregate as well as a binder, and the print solution may additionally or alternately include a binder in some embodiments. Upon contact, the print solution dissolves the active components of the powder system, which may include particulate adhesive material and/or a rapid solidification binder. The rapid solidification binder may be a silicate-based binder, as described below, but could also include any inorganic or organic binder that can be quickly initiated, such as by an acid gas (e.g. CO₂). The wetting action converts the once dry powder layer into a hydrated binder in contact with the aggregate and fillers and the layer below.

In one embodiment, where the powder layer and/or the print solution includes an acid gas-curable binder (such as a silicate), the method then utilizes an acid gas (e.g. CO₂) to quickly react with the hydrated silicate after the application of the print solution. The acid gas may be any type of chemically active gas which is acidic and/or forms an acid upon contact with the gas-curable binder, and it is understood that different acid-curable binders may be curable using different types of acid gases. As described below, alkali silicate binders may be cured using CO₂ in one embodiment. The acid gas can be introduced into contact with the binder by pumping into the head space above the print or directly onto the powder through the print head. This process is then repeated, layer-by-layer, until the 3D body is completely fabricated from the addition of successive layers. One embodiment of this process is described in greater detail below. The acid gas curing process can be used to provide a more rapid rate of cure. Normally, the application of an aqueous solution to a powder bed would start to distort the pattern due to density differences between the hydrated powder and dry powder. By quickly reacting the dry powder to a solid state, the present method can reduce the amount of support material needed and may increase the accuracy of the print.

The powder that was not contacted by the print solution is left in its powdered state and is able to be readily removed after all of the required layers of the print have completed and even recycled. The non-hydrated powder also acts to secure the printed material until de-powdering.

The printed part is then removed from the printer and can either be utilized directly or undergo post processing such as thermal treatment (e.g. convective oven, Microwave), polymer infusion, or other techniques, to achieve higher strength. Advantageously, the part is in at least a partially-hardened state after the acid curing, which allows removal of the part from the printer without further curing/drying steps. This, in turn, allows for more rapid fabrication of parts, among other benefits.

Further, the utilization of multiple binder systems allows the solubility (in water or other solvent) of the binder of the dry print material to be custom tailored, to produce cores with soluble and/or insoluble binders, including water soluble or water insoluble binders. This is accomplished by utilizing a selected mixture of organic dehydration hardening binders and the inorganic silicates. It is understood that “water soluble” binder systems, as described herein, include systems having varying degrees of water-solubility, and generally refers to binder systems with sufficient water-solubility to allow partial or complete removal of the core by application of water.

As stated above, the powder composition may include a filler or aggregate material, which may include one or more of the following: Plaster of Paris, sand, graphite fibers or other carbon, fly ash, fly-ash components, glass spheres or beads, hollow-spheres or cenospheres, Talcum, calcium carbonate, fused silica, garnet, sodium chloride, alumina (Al₂O₃) and/or aluminum tri-hydrate, and combinations thereof, as well as other known fillers and any aggregate materials described elsewhere herein. In one embodiment, the aggregate may be a low-density aggregate material. The powder composition may include an aggregate powder with a mean particle size of between 20 and 150 microns in one embodiment, between 30 and 50 microns in another embodiment, and about 40 microns in a further embodiment. The final powder may have a volume fraction ranging from about 50% to about 99% and a mean, maximum particle aspect ratio of less than 3:1. The powder composition may further include additives that enhance thermal conductivity, electrical conductivity and/or mechanical strength. Such additives may include, but are not limited to, carbon, silicon or metal oxide derived materials in powder or fibrous form, and may range from about 0.1% to about 25% by weight. Any additives described above in connection with compositions for mold-based processing can be used as well.

Additionally, a number of different binders and binder systems can be used in connection with the compositions and methods described above, including inorganic binders, organic binders, and organic-inorganic hybrid binder systems, which may include water-soluble or other solvent-soluble binders to assist with tool removal.

Inorganic Binders

Silicate binders, including alkali silicates, can be used in connection with the compositions and methods of certain embodiments utilizing 3D printing techniques. In one embodiment, alkali silicates, such as sodium silicates (e.g. Na₂SiO₃), potassium silicates (e.g. K₂SiO₃), etc., can provide immediate strength to the print head hydrated powders through reaction with an acid, such as CO₂ gas. Common industrial solid phase silicates include (Kasolv, Sodium Silicate GD, etc.) produced by the Potters Group. These anhydrous forms of the liquid silicates come in a range of alkalinities and can be utilized in the printing powders from 1-90 wt. %, in various embodiments. By adjusting the amount of caustic (NaO, KO), the relative solubility of the silicate powder can be modified. Due to the desired rapid response of the binder, a high caustic ratio may be used in some embodiments to assist in achieving this effect. In one embodiment, an alkali silicate with an alkali caustic to silicate ratio of 3:1 is utilized, which can provide good performance solubility of the silicate powder, so that the silicate powder is able to readily react with the acid gas for precipitation. If an alumina silicate based aggregate is used in the powder composition, the SiO that is precipitated from the acid/base neutralization forms immediate vicinity bonds with the aggregate surrounding the binder (such as an alumina-silicate based aggregate), leaving an insoluble matrix. Dehydration of the alkali silicate can also produce a bound matrix without the administration of the acid gas, which leaves the binder matrix water soluble. By itself, the alkali silicate based powder system is fully capable of rapid production of an insoluble printed part. Immediately upon removal from the printer, the part may either be resin infused to for higher strength or completely dried for metal casting. Parts produced using this binder and aggregate combination in a 3D printing apparatus are capable of being used as tools in material production processes that reach temperatures of at least 500° C., and can be removed using steam and/or chemical methods.

In one embodiment, a powder composition of alkali silicate (1-90%) and an aggregate such as fused silica could be used in a 3D printing process. In another embodiment, some or all of the alkali silicate could be provided in aqueous solution. One example embodiment of a mixture utilizing a water insoluble binder system for use in 3D printing applications includes, by weight, 3-50% alkali silicate, and about 50-97% aggregate (e.g. cenospheres, glass spheres, fused silica, etc.). Another example of a mixture utilizing a water insoluble binder system for use in 3D printing applications includes, by weight, about 15% alkali silicate, and about 85% cenospheres, fused silica or other aggregate.

Incorporation of a water soluble secondary binder, such as an organic binder in a hybrid binder system, allows both properties of rapid removal and water solubility to be obtained, as described below. In one embodiment, one or more silicate binders may be used to enable rapid removal of the core, and water solubility can be achieved by mixing other water soluble binders in the powder bed (or in the print solution) and waiting for the water soluble binder to solidify, such as by dehydration or applying heat to aid in dehydration.

Organic Binders

Organic water soluble binder systems can be used to provide greater final strength to the tooling material in some embodiments utilizing 3D printing techniques. Examples of individual binder components that can be incorporated in the material are described below. Each component can be used in concentrations of between 0 and 80 wt. %.

Polyvinyl pyrrolidone (PVP) is one organic binder that can be used in connection with the compositions and methods of certain embodiments. The inclusion of PVP as a water soluble binder can create significant strength for the final printed part upon dehydration. PVP is added in relative proportion to the silicate to insure solubility after acid gas cure. In some embodiments, binder systems using PVP are able to achieve strength values that are much higher than a silicate-only system. Utilizing PVP in a binder system can also be advantageous due to its ability to operate at temperatures in excess of 170° C. without significant softening and without losing its water solubility. These properties can be especially beneficial for the fabrication of printed cores for producing hollow plastic or re-enforced composites. Hybrid binder systems can be utilized containing PVP and silicates alone, or with various other additives, as described below.

Salts of carboxymethyl cellulose (SCMC) are additional organic binders that can be used in connection with the compositions and methods of certain embodiments. SCMC combine good strength as a binding agent and the ability to dissolve in water or equivalent polar solvents. In one embodiment, a hybrid mixture containing between 0.5 and 40 wt. % SCMC and a ratio of solid alkali silicate, with the remainder being a filler or aggregate, such as carbon, sand, or cenospheres, can be used for the production of water soluble tooling materials. The SCMC can contain several cations such as, but not limited to, H⁺, Na⁺, K⁺Ca²⁺, etc.). Further, in one embodiment, the degree of substitution of carboxymethyl cellulose groups per anhydroglucose chain is between 0.5 and 0.9. Several commercial variations of compositions are available under the trademark Peridur®. These systems can exhibit increased binder performance through slight increases in pH. Any OH-donor is acceptable for pH adjustment. The SCMC binder can be added to an aggregate, such as a cenosphere media equivalent to the above PVP process, but instead of being burnt out for removal, it can be re-hydrolyzed and broken down with water.

Proteins are another type of organic binders that can be used in connection with the compositions and methods of certain embodiments. Proteins can be used as water soluble binders for the formation of high strength mandrels, when combined with water and filler. The binder can be removed at room temperature with the addition of water and subsequent re-hydration of the protein. In one embodiment, the protein content of the binder material is between 0 and 60 wt. % of the total filler weight. Protein based dehydration binders can present a very environmentally friendly solution to achieve a tool that has appreciable strength. This binder may require dehydration to reach ultimate strength, and as such may not be rapidly removable from the printer unless coupled with a rapid-set binder system, such as a silicate system. In one embodiment, a protein binder can be used in combination with an alkali silicate binder to form a hybrid binder system that is water soluble after curing.

As described above, hybrid binder systems, utilizing two or more organic and/or inorganic binder materials, can be used in certain embodiments to achieve advantageous results. In one embodiment, a hybrid binder system includes a mixture of at least one acid-curable inorganic binder (e.g., alkali silicates) and one water-soluble or other soluble organic binder (e.g., PVP). The hydration of such a dual or multiple binder powder by the printing solution produces a two-fold reaction. First, water in the printing solution hydrates the alkali silicate into a partial solution phase, which creates free hydroxides in the powder binder mixture. At the same time, the water rehydrates the organic binder so that it can unravel and spread out upon hydration and adhere to its surroundings, including the neighboring compounds or aggregate in the powder. The organic binder may require dehydration again to achieve desired strength for removal from the printer. At this point, the high pH regions of the alkali silicate are readily available for reaction with any acidic components, which can be delivered or introduced into the matrix in several different ways. One such method, described above, is to administer an acid gas through a gas solid reaction with the surface powder layer. This simplifies the introduction of alternative proton donors into the powder that may weaken the final part. Introduction of an acid-releasing compound in the powder is also an option. In one embodiment, the silicate to organic ratio is proportional to the specific amount of organic used. Normally, due to the low solubility of the silicate powder, a 1:1 to 3:1 (by wt.) ratio of silicate binder to organic binder is needed to provide sufficient rapid curing. However, in other embodiments, other ratios may be used. Once the silicate binder has been cured, the mandrel still contains the hydration waters contained both in excess of the silicate and within the hydrated organic binder. Full strength can be achieved by dehydration of the part after removal from the printer. This can be achieved by many techniques, including convective heating, microwave, or other heating or dehydrating techniques.

One example embodiment of a mixture utilizing a water soluble hybrid binder system for use in 3D printing applications includes, by weight, about 1-55% alkali silicate (e.g. sodium and/or potassium silicate), about 3-70% PVP, and about 20-90% aggregate (e.g. cenospheres, glass spheres, etc.). Another example of a mixture utilizing a water soluble hybrid binder system for use in 3D printing applications includes from about 1% to about 10% by weight PVP, from about 1% to about 30% by weight sodium and/or potassium silicate, and from about 69% to about 89% by weight aggregate. Another example of a mixture utilizing a water soluble hybrid binder system for use in 3D printing applications includes, by weight, about 15% Kasolv (potassium silicate), about 30% PVP, and about 55% aggregate (e.g. cenospheres). A further example of a mixture utilizing a water soluble hybrid binder system for use in 3D printing applications includes, by weight, about 5-20% alkali silicate, about 5-20% PVP, and about 60-90% aggregate. It is understood that any binder composition for use in 3D printing methods can incorporate any of the additives described above with respect to the mold-based systems and methods.

Other applications of the hybrid system utilize an organic/inorganic surface coating composition to inhibit complete formation of insoluble bonds between aggregate particles, which can ensure some degree of water solubility. This allows strong insoluble bonds (e.g. cement) to form in a portion of the material while holding the rest together with the water soluble polymer. The resultant mandrel is comprised of a weakened water soluble polymer binder reinforced with a cement type inorganic binder, and the mandrel can be washed out with water after use, due to breakdown of the water soluble binder. This technique can be used with any of the binder compositions described herein.

In a further embodiment, a hybrid organic/inorganic system may be used that is not acid curable. For example, a binder system may be used which allows water to be absolved after forming the mandrel material, which can present difficulties in existing organic systems. In one embodiment, an anhydrous salt (e.g., CaCl) can be incorporated into the water soluble polymer system (e.g. PVP) to act as a drying agent by chemically drying the media. This internal drying of the media from the inside reduces or eliminates the need for heating to dry the media in the printer. After this step, the partially dehydrated organic polymer has sufficient strength to be removed from the printer and further dehydrated outside the printer.

It is understood that, in some embodiments, the compositions disclosed above for use in mold-based methods can be used in 3D printing-based methods, and likewise, the compositions disclosed above for use in 3D printing-based methods can be used in mold-based methods, as well as other methods for producing tooling materials. Certain processing techniques can similarly be used in all types of disclosed methods.

The following description references FIG. 9, which is a stepwise description of one embodiment of a powder 3D printing method 800 with rapid curing, as described above. In this embodiment, a binder system using at least one acid-curable binder component (e.g. alkali silicate) is used, and at least one additional binder component may also be used, such as an organic water soluble binder component. Such binder components may be included in a powder composition that also includes at least one aggregate material, as described above. As also described above, certain components of the binder system, including additives, may be included in a print solution.

At step 801, a roller 1 is utilized to roll out a thin layer of fresh powder 2 from a supply reservoir. After being rolled to a predefined thickness, an inkjet printer head 3 supplies an aqueous print solution 4 onto the fresh powder bed 2, leaving behind partially hydrated powder 5 in a predefined cross sectional shape, at step 802. The function of the printer head 3, and the resultant shape, may be patterned or guided by process software, and it is understood that the printer head 3 may be movable in a plurality of different directions in three dimensions. The print solution 4 may include at least one binder material and/or other dissolved components in one embodiment, as described above, or may contain only water in another embodiment. In one embodiment, the print solution 4 may include 10-40% by volume of fluid binder ingredients. After hydration, an acid gas 6 (e.g. CO₂) supplied in the head space above the hydrated powder 5 is able to react with the acid-curable binder component(s) to produce a partially solidified hydrated layer 8 containing at least partially solidified powder 7, at step 803. The acid gas 6 may be supplied from a port or nozzle (not shown) connected to the printer head 3 in one embodiment. The acid gas 6 may be deposited on the hydrated powder 5 about 0.01-10 seconds (about 0.5 seconds in one embodiment) after the print solution 4 is deposited on the dry powder bed 2. The process then repeats at step 804, by using the roller 1 to roll a new layer of powder 2 on top of the partially solidified hydrated layer 8. The print head 3 then places another predefined pattern of print solution 4 on top of the fresh powder 2 to form another hydrated powder layer 5, which may also partially hydrate the previous layer 8, at step 805. Again, the acid gas 6 is supplied in the head space, to react with the acid-curable binder component(s) to form a second partially solidified hydrated layer 9 with solidified powder 7 that is intimately connected to the solidified powder 7 previous layer 8, at step 806. The process can be repeated as necessary to complete the 3D part 10, which is formed of a plurality of solidified powder layers 7 intimately connected together. After the desired shape is created, the formed part 10 can be removed in a partially-hardened condition from the left over non-hydrated powder 2, at step 807. The part 10 can then be dehydrated 11, such as by utilizing microwave, convective or vacuum assistance, for moisture removal 12, at step 808. The non hydrated powder 2 can then be recycled for the next print.

A part produced using 3D printing methods, such as the part 10 in FIG. 9, may be used as a mandrel, core, mold, or other tooling for production of materials, including polymer and/or composite materials, as similarly described above with respect to mandrels produced using mold based methods, such as in FIG. 7. The use of the 3D printing process permits the production of tooling that has very complex geometries. The cured part may have a coefficient of thermal expansion between the range of 0.5-9.0×10⁻⁶ mm/mm/° C., a specific gravity of between about 0.26 and 2.6, and an ultimate compressive strength at 22° C. of no less than 0.25 MPa, and greater than or equal to 5 MPa in one embodiment. The part may also be capable of exposure to autoclave conditions in excess of 185° C. and 0.75 MPa without substantial deformation or mechanical failure.

The products, materials, methods, and machines disclosed herein provide several advantages over prior products, materials, methods, and machines. For example, in certain embodiments where a water-soluble binder is used, the mandrel may easily and rapidly be removed from the composite structure in less than a minute or two simply by immersing the composite structure and mandrel in a plain water bath or by subjecting then to steam. A particular advantage of the present invention is that machining and finishing operations on the mandrel can be eliminated and the mandrel may be used for forming of either interior or exterior complex product surfaces. Additionally, the mandrel is dimensionally stable and is able to withstand high pressures. Still other benefits exist and are identified herein.

Several alternative embodiments and examples have been described and illustrated herein. A person of ordinary skill in the art would appreciate the features of the individual embodiments, and the possible combinations and variations of the components. A person of ordinary skill in the art would further appreciate that any of the embodiments could be provided in any combination with the other embodiments disclosed herein. It is understood that the invention may be embodied in other specific forms without departing from the spirit or central characteristics thereof. The present examples and embodiments, therefore, are to be considered in all respects as illustrative and not restrictive, and the invention is not to be limited to the details given herein. All component percentages described herein refer to weight percentages, unless specifically identified otherwise. The term “plurality,” as used herein, indicates any number greater than one, either disjunctively or conjunctively, as necessary, up to an infinite number. Accordingly, while the specific embodiments have been illustrated and described, numerous modifications come to mind without significantly departing from the spirit of the invention and the scope of protection is only limited by the scope of the accompanying claims. 

1. A composition for use in manufacturing a water-soluble tooling material, comprising: an organic binder material that is water soluble after curing; a water-soluble alkali silicate binder material that is curable by acid gas curing to produce a water-insoluble structure; and an aggregate material.
 2. The composition of claim 1, wherein the organic binder material comprises polyvinylpyrrolidone and the inorganic binder material comprises at least one of sodium silicate and potassium silicate.
 3. The composition of claim 1, wherein the composition is provided as a powdered mixture configured for use in a 3D printing apparatus.
 4. The composition of claim 3, wherein the powdered mixture has a particle size of between about 20 microns and about 150 microns.
 5. The composition of claim 3, wherein the powdered mixture has a volume fraction of powder from about 50% to about 99% by weight and a mean maximum particle aspect ratio of less than 3:1.
 6. The composition of claim 1, wherein the composition comprises, by weight, from about 1% to about 10% polyvinylpyrrolidone and from about 1% to about 30% alkali silicate.
 7. The composition of claim 1, wherein the composition comprises, by weight, about 1-55% alkali silicate, about 3-70% polyvinylpyrrolidone, and about 20-90% aggregate material.
 8. The composition of claim 1, wherein the composition comprises, by weight, about 15% potassium silicate, about 30% polyvinylpyrrolidone, and about 55% aggregate material.
 9. The composition of claim 1, wherein the aggregate material is selected from a group consisting of: Plaster of Paris, sand, graphite fibers or other carbon, fly ash, fly-ash components, glass spheres or beads, hollow-spheres, cenospheres, talcum, calcium carbonate, fused silica, garnet, sodium chloride, alumina, aluminum tri-hydrate, and combinations thereof.
 10. The composition of claim 1, wherein the organic binder material comprises a protein.
 11. The composition of claim 1, wherein the aggregate material comprises cenospheres.
 12. The composition of claim 1, wherein the organic binder material comprises salts of carboxymethyl cellulose, of which the composition includes between about 0.5% and 40% by weight.
 13. The composition of claim 12, wherein the salts of carboxymethyl cellulose include at least one cation selected from a group consisting of: H⁺, Na⁺, K⁺ Ca²⁺, and combinations thereof, and a degree of substitution of carboxymethyl cellulose groups per anhydroglucose chain is between 0.5 and 0.9.
 14. The composition of claim 1, wherein the alkali silicate binder material has an alkali caustic to silicate ratio of 3:1.
 15. The composition of claim 1, wherein the composition has a ratio of alkali silicate binder to organic binder of about 1:1 to 3:1, by weight.
 16. The composition of claim 1, wherein the at least one of the organic binder material and the alkali silicate binder material is provided in aqueous solution.
 17. The composition of claim 1, wherein the alkali silicate binder material is present in sufficient amount to enable handling of a part produced from the composition after acid gas curing and without curing of the organic binder material, and wherein the organic binder material is present in sufficient amount to enable the part to be removed completely using application of water.
 18. A powdered mixture for use in manufacturing a water-soluble tooling material using a 3D printing apparatus, the composition comprising, by weight: from about 1% to about 55% of a water-soluble alkali silicate that is acid-curable to produce a water-insoluble structure, from about 3% to about 70% polyvinylpyrrolidone, and from about 20 to about 90% aggregate material, wherein the powdered mixture has a particle size of between about 20 microns and about 150 microns.
 19. A composition for use in manufacturing a water-soluble tooling material using a 3D printing apparatus, the composition comprising, by weight: about 5-20% alkali silicate, about 5-20% polyvinylpyrrolidone, and about 60-90% aggregate.
 20. The composition of claim 19, wherein at least one of the alkali silicate and the polyvinylpyrrolidone is provided in aqueous solution.
 21. A composition for use in manufacturing a water-soluble tooling material using a 3D printing apparatus, the composition comprising, by weight: about 3-50% alkali silicate and about 50-97% aggregate.
 22. The composition of claim 21, wherein the composition comprises, by weight, about 15% alkali silicate, and about 85% aggregate.
 23. The composition of claim 21, wherein the aggregate is fused silica.
 24. The composition of claim 21, wherein the alkali silicate is potassium silicate.
 25. The composition of claim 21, wherein the alkali silicate has an alkali caustic to silicate ratio of 3:1. 